Water-insoluble azo dyestuffs and fiber dyed therewith



Patented June 4, 1940 UNITED STATES WATER-INSOLUBLE AZO DYESTUFFS AND FIBER DYED THEREVVITH Arthur Zitscher,

I Schmitt, Darmstadt,. and

Frankfort-on-the-Main-Hochst, Germany,

General Aniline & Film Corporation,

signors to Kronberg in Taunus, Robert Herbert Kracker,

a corporation of Delaware No Drawing.

Application rial No. 241,692. In Germany November 21, 1938, Se-

September 11,

8 Claims (01. 260-193) The present invention relates to water-insoluble azo dyestuffs and to fiber dyed therewith; more particularly it relates to dyestuffs corresponding to the .following general formula:

wherein R represents an alkyl radical, X and Y stand for halogen or alkoxy, Y meaning alkoxy in case X stands for halogen, and halogen in case X stands for-'alkoxy, and wherein the benzene nucleus I may be further substituted by halogen, alkyl, alkoxyor aryloxy groups.

This application is a continuation-impart of our application Serial No. 39,500, filed September 6, 1935', which has become abandoned.

We have found that valuable water-insoluble azo dyestuffs are obtainable by coupling in substancefon the fiber or on a substratum adapted for the production of lakes arylides of acetoacetic' acid of the following formula:

IfELCOUHaGQC/Ha an alkyl radical, X and Y alkoxy, Y meaning alkoxy and halogen in diam-compounds from mono-amines of the benzene series which contain at least one halogen atom and, if desired, halogen, alkyl, alkoxy or aryloxy groups as substituents.

When produced in substance, the new dyestuffs may be used for the preparation of valuable pigments, but they may also be used with advantage for the production of insoluble dyestuffs on the fiber according to the ice-colormethod or one of the usual printing methods, for instance, in direct printing, or according to the known nitrosamine-printing-process or the like.

The yellow dyestuffs thus obtained are distinguished by their good all around fastness properties, particularly by unobjectionable fastness to soaping; a great number of them have also a high fastness to light.

The following examples serve to illustrate the invention, but they are not intended to limit it thereto, the parts being by weight, unless otherwise stated:

(ll 17.6 parts of l-amino-3 -methyl-2A-dichlorobenzene are diazotized in the usual manner and the diazo-solution is coupled with a solution'of 32.4 parts 2.5-dimethoxy-l-bromobenzene in dilute caustic soda solution to which there has been added Turkey red oil and the quantity of. sodium acetate which is necessary to bind the mineral acid in excess. The separated dyestuff is filtered off and washed well. When produced in the usual manner, advantageously in the form of a paste, on a substratum, it yields a greenish-yellow lake of high fastness to light. The dyestufi .has the following formula:

of 1- (acetoacetyl-amino) (2) Bleached cotton yarn is grounded in a solution containing per liter 6 grams of l-(acetoacetyl-amino)-2.5-dimethoxy--chlorobenzene, 12 cc. of caustic soda solution of 34 B.,

5 cc. of Turkey red oil and ethoxy- 1-amino-2-chloro-benzene (4) Desized and bleached cotton piece goods are printed with the following paste:

20 grams of 2-methyl-4.5dichlorobenze-1-nitrosamine-sodium, 24 grams of l-(acetoacetyl-amino) oxy--chlorobenzene,

-2.5-dimethl f 4 00 grams of sodium ChlOIlde, 30 grgfids of caustic soda solution 0 3 Be thoroughly squeezed and developed in a diazo- T I solution neutralized with sodium acetate and con- 20 ggg i key d 011 are/Starred Into a n taming per liter the diazo compound from 50 grams of Water dissolved in grams 0f m m y e 356 grams of Warm water and made up with Z6118, rinsed and OaDB 1 1a boilingsolu- 500 grams of neutral starch tragacanth thickt on C ta D liter ening to l'kilo of printing color. I 1 gram of sodium carbonate, 15 3 grams f soap and After drying, the printed material is steamed 05 gram f sodium h dro ulfit in a moist state for 3 minutes or exposed to the air over-night and thereupon passed at 80 C. to greentsh yellow dyemg thus obtamed. has 90 C. through a solution containing cc. of Vely good fastness to hght' acetic acid of 50% strength per liter, rinsed and 20 20 The dyestuff may be also produced on other soaped vegetable fibers, on natlve cellulose, as, for 1D.- A yellow print of Very good fastness to Wash stance, linen or on regenerated cellulose, as, for mg is obtained. v

. riteit on which. a more reddlsh dyeing 1s obtained. p n d W th he followmg paste a I (3) Desized and b eached COtTJOH piece goods 36 grams of the disodium salt of the diazoamino are padded on a. foulard in asolution containing om und fr m p2-m thy1-4-ch1oro-1-diper liter j azobenzene and. 1-amino-2-carboxyben- 15 grams of l-(aceto-acetyl-amino)-2.4-diacld 3 0 methoxywmorobenzene 24 grams 4of l-(acetoacetylamino) 2.5-d1meth- 22.5 cc. of caustic soda solution of 34 B. and f o 20 cc of Turkey red on 30 grams of caustic soda solution of 34 Be. and The grounded and drled materlal 18 passed 20 grams of- Turkey red oil are stirred into a v. through a diazo-sclution obtained according to paste t he f ll wl n l 50 grams of Water and dissolved in 11 grams f 1 g t 5 340 grams of Warm water" and made up with Zane hydrochloride are dissolved in 500 grams of neutral starch tragacanth thick- 12 cc. of hydrochloric acid of 20 B. and emng 1 1 o 40 200 cc of Water the solution is cooled to 5 C d 1 f After drying the printed material is steamed 4 3 an IFLZO fif 1 Th 1n a rapid ager for 5 minutes 1n the presence grams 3 g m ere of acetic acid vapor and formic acid vapor 8 zg g g fi j Sodium acetate and thereupon rinsed and soaped. A greenish yeli t r l i l .4 20 cc. of acetic acid of strength and the Egg 525 of Ve y good fastness propertles whole 18 made up to 1 hter' The process may be carried out in the same The material is then exposed to the air for manner with other diazo compounds and other a. short time, rinsed several times with cold water arylides of aceto-acetic acid of this series. 50 and finally soaped at boiling temperature. The following table indicates a number of tints 99 A yellow dyeing of very good fastness to light of some other azo dyestufis obtainable accordis obtained. ing to the present invention:

Aceto-acetyl compound of- Coupled with the disco-compound of- Tint l-amino-Z.5-dimethoxy-4-chlorobenzene l-amino-2-methyl-3-chlorobenzene Greenish yellow.

- do l-amino-3-methyl-2.4-dichlorobenzene. Clearlemon-yellow,

. do 1-amino-3-methyl-4.6-dichlnrobenzene Yellow.

l-amino-l-methyl-B-chlorobenzene Lemon-yellow. l-amino-4-methyl-2.5-dichl0robenzene- Yellow. 1-amino-2.5-diethoxy-4-chlorobenzene Do. l-amino-2-chlorobenzene Greenish yellow. l-amino-Z-methyl-chlorobonze Yellow. Lamina-2.5-dichlorobenzene Do. l-amiuo2-methyl-3-chlorobenzene Greenish yellow. l-amino-2.3.4-trichlorobenzene Yellow. 1-amino-2-methoxy-5-chlorobenzene; Greenish yellow. l-aminoZ-phenoxy-achlorobenzene Reddish yellow. l-amino-2-(4-chlorphenoxy)-5-chlorobenzene Yellow. l-amino-Z-(2-methylphenoxy)-5-chlorobenzene Reddish yellow. l-amino-2-(4-methoxyphenoxy) 5- chloroben- Do.

Z6116 1-amino-2-(naphthyl-W-hydroxy)-5-ch1oroben- D0. lisi o-mcthyM-bromobenzene Yellow. -amino-2-methyl-5-bromobenzene Greenish yellow. l-amino-Z-methyl--mdobenzene Yellow. 1-am1no-4-methyl-2 3-d1chlorobe D0. 1-am1no-2-methyl-5-chloro-4 Do;

-amino-2-methoxy-3-ch1orobenze Greenish yellow. l-amino-4-meth0Xy-3-ch1orobenzene. Do. 1-amino-2-ethoXy-5-chlorobenzene; Yellow. 1-amino-2-methoxy-4.5-dichl D Greenish yellow.

Since an object of the present invention is to provide dyestuffs of good fastness :properties which dyestuffs are insoluble in water and alkalies, it is to be understood that the aromatic nuclei of the general formulae appearing in the appended claims do not contain any substituents which are known to render organic compounds soluble in water or alkalies and to tend to depreciate the fastness of the dyestuffs to alkalies. Substituents of this kind are, for instance, the sulfonic acid and the carboxylic acid group.

We claim:

l. The water-insoluble azo dyestuffs oi the following general formula:

N=N halogen 11 oon-oo-on.

halogen wherein R represents a member of the group consisting of methyl and ethyl, X stands for one of the group consisting of chlorine, methyl, methoxy and ethoxy, Y for one of the group consisting of hydrogen and methyl and Z for one of the group consisting of hydro-gen and chlorine, the benzene nucleus or. always containing one methyl group and two halogen atoms, yielding, when produced on the fiber, yellow dyeings of good fastness properties, particularly of very good fastness to soaping and to light.

2. The water-insoluble azo dyestufis of the 0 following general formula:

01 wherein X stands for one of the group consisting of chlorine, methyl, methoxy and ethoxy, Y stands for one of the group consisting of hydro- 1-amino-3-rnethyl-ltdxohlorobenzen l-amino-Z-methoxy-fi'chlorobenzene. l-aminol-methyl-2. .i-dichlorohenzene. l-amino-2-ethoxy-4hromo-5-chlorob enzene l-amino-Z-meth oxyfi-chlorob enzene Lamino-2-methyl Zi-chlorohenzeno l-amino-2-m ethyl-4-br omobenzene 1-amino-2-mcthyl-3A dichlorobenzene l-amino-amethyli. S-dichlorobenzene l-amino-amethyl-e.ddichlorobenzene. l-amino-4-methyl-2. 5 dichlorobenzene l-amino-Z-phen oxy-3-chlorobenzene, l-amino-2methoxy-4. 5-dichlorobenzene l-amino-Z-methyl--bromo-Evchlor ob enzen l-amino-2.4-dlchlorobenzene l-amino-ZA.S-trichlorobenzene 1-amina2-methoxy-4.5-dichlorobenze 1-amino-%methoxy-4rbr0mo-5- h1orobenzene l-aminaZ-methyl-ifi-dichlorob enzene 1-amino-3-methyl-2.4-dichlorob enzene l-amino-2. l-dichlorobenzene l-amind 2.4. fi-trichlorobenzene 1-amin0-2-meth oxy-4. E-dichlorob enzene led with the diam-compound 0l Yellow. Greenish yellow. 5

Yellow Do.

D0. Gteenish yellow.

Reddish yellow. Yellow. Reddish yellow. Groenish yellow. Yellow.

Do. Greenish yellow. Reddish yellow.

Yellow.

Do. 'Reddish yellow.

Yellow. Greenish yellow. Orange yellow. Greenish yellow.

gen and methyl and Z for one of the group consisting of hydrogen and chlorine, the benzene nucleus at always containing one methyl group and two chlorine atoms, yielding, when produced on the fiber, yellow dyeings of good fastness properties, particularly of very good fastness to soaping and to light. I 3. The water-insoluble azo dyestuff of the following formula:

N,=N Cl nH-oo-cH-co-om OCH:

HUGO 1 yielding, when produced on the fiber, clear lemon-yellow dyeings of good fastness properties, particularly of very good fastness to soaping and to light.

4. The water-insoluble azo dyestufi of the following formula:

N=N c1 NHoo-cH-o0-oH| o1 -OCH:

o1 yielding, when produced on the fiber, yellow dyeings of good iastness properties, particularly of very good fastness to soaping and to light.

5. Fiber dyed with the water-insoluble azo dyestuffs as claimed in claim 1'.

6. Fiber dyed with the water-insoluble azo 'dyestufis as claimed in claim 2. 7. Fiber dyed with the water-insoluble azo dyestuff as claimed in claim 3.

8. Fiber dyed with the water-insoluble azo dyestuff as claimed in claim 4.

ARTHUR ZITSCHlER. ROBERT SCHMIT'I'. HERBERT KRACKER. 

